The invention relates to the technical field of the intermediates for the preparation of active substances, in particular herbicidally active sulfonylureas.
It is known that aromatic amines can be reacted to give sulfonic acid derivatives such as sulfochlorides and further to give sulfonamides which, in turn, can be employed for the preparation of herbicidally active sulfonylureas (Meerwein et al., Chem. Berichte 90, 841-852 (1957) and EP-A-574418).
A substituted anthranilic acid is known from J. Med. Chem. 1986, Vol. 29, No. 4, page 585 as intermediate for the preparation of certain anhydrides which are suitable for inactivating trypsin-like enzymes.
It was an object to provide novel chemical compounds which are suitable for the preparation of herbicidally active sulfonylureas. Surprisingly, this object is achieved by compounds of the formula (I) 
in which
R1 is H, (C1-C8)alkyl, (C3-C8)alkenyl or (C3-C8)alkynyl, where the last 3 radicals are unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkyl]carbonyl or [(C1-C4)alkoxy]carbonyl,
R2, R3 independently of one another are H or acyl, preferably H,
R4, R5 are H,
R6 is H or (C1-C8)alkyl which is unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, [(C1-C4)alkyl]carbonyl or CN, preferably H,
R7 is (C1-C8)alkyl, (C3-C8)alkenyl or (C3-C8)alkynyl which are unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy or (C1-C4)alkylthio, or R7 is (C6-C14)aryl (for example phenyl) which is unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, NO2, CN, (C1-C4)alkyl, (C1-C4)haloalkyl or (C1-C4)alkoxy, or R7 is mono- or di-(C1-C8)alkylamino which is unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkylsulfinyl, (C1-C4)alkylsulfonyl, [(C1-C4)alkyl]carbonyl, [(C1-C4)alkoxy]carbonyl or CN, or
R6 and R7 together form a chain of the formula xe2x80x94(CH2)mBm1xe2x80x94 which is unsubstituted or substituted, for example by one or more (C1-C4)alkyl radicals, and where m=2, 3 or 4, m1=0 or 1 and Bxe2x95x90CO or SO2,
R8 radicals, are identical or different and are (C1-C4)alkyl, (C1-C4)alkoxy, [(C1-C4)alkyl]carbonyl or [(C1-C4)alkoxy]carbonyl which are unsubstituted or substituted, for example by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy, (C1-C4)alkylthio, [(C1-C4)alkyl]carbonyl or [(C1-C4)alkoxy]carbonyl, or R8 is halogen or NH2, and
n is 0, 1, 2 or 3, preferably 0.
Preferred compounds of the formula (I) are those in which
R1 is H or (C1-C4)alkyl, preferably (C1-C4)alkyl,
R2 and R3 are H,
R4 and R5 are H,
R6 is H,
R7 is (C1-C4)alkyl, and
n is 0.
Compounds of the formula (I) which are of particular importance are those in which the group CR4R5xe2x80x94NR6xe2x80x94SO2xe2x80x94R7 is in the para position relative to the group xe2x80x94COxe2x80x94OR1. If together form a chain of the formula xe2x80x94(CH2)mBm1xe2x80x94 and m1=1, it is preferable that B is bound to the nitrogen atom which has R6 attached to it.
Examples of compounds of the formula (I) are listed in table 1 hereinbelow:
If the term acyl is used in the present description, it denotes the radical of an organic acid which arises formally by eliminating an OH group from the organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
An acyl radical is preferably formyl or acyl from the group consisting of COxe2x80x94Rx, CSxe2x80x94Rx, COxe2x80x94ORx, CSxe2x80x94ORx, CSxe2x80x94SRx, Crxxe2x95x90NRY, SORYor SO2Y, where Rx and RY are each a C1-C10-hydrocarbon radical such as C1-C10-alkyl or C6-C10-aryl, each of which is unsubstituted or substituted, for example by one or more substituents selected from the group consisting of halogen such as F, Cl, Br, I, alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano or alkylthio, or acyl is aminocarbonyl or aminosulfonyl, the two last-mentioned radicals being unsubstituted, N-monosubstituted or N,N-disubstituted, for example by substituents from the group consisting of alkyl or aryl. Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C1-C4)alkylcarbonyl, phenylcarbonyl, it being possible for the phenyl ring to be substituted, or alkyloxycarbonyl, such as (C1-C4) alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, such as (C1-C4) alkylsulfonyl, alkylsulfinyl, such as C1-C4(alkylsulfinyl), N-alkyl-1-iminoalkyl, such as Nxe2x80x94(C1-C4)-1-imino-(C1-C4)alkyl and other radicals of organic acids.
In formula (I) and the general formulae used hereinbelow, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy and alkylthio and the corresponding substituted radicals can be in each case straight-chain or branched in the carbon skeleton. Unless specified otherwise, the lower carbon skeletons, for example those having 1 to 4 carbon atoms, are preferred amongst these radicals. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl and the like, are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyls, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meanings of the possible unsaturated radicals which correspond to the alkyl radicals; for example alkenyl is allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
Alkenyl, for example in the form xe2x80x9c(C3-C8)alkenylxe2x80x9d, is preferably an alkenyl radical having 3 to 8 carbon atoms in which the double bond is not positioned at the carbon atom which is linked to the remaining moiety of the compound (I) (xe2x80x9cylxe2x80x9d position). This also applies analogously to alkynyl radicals.
Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl, each of which is partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCl2, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2Cl; this also applies analogously to haloalkenyloxy and other halogen-substituted radicals.
Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, for example phenyl, are, for example, a substituted radical which is derived from the unsubstituted skeleton, the substituents being, for example, one or more, preferably 1, 2 or 3, radicals selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic radicals which correspond to the abovementioned saturated hydrocarbon-containing radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy and the like. In the case of radicals with carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Preferred are, as a rule, substituents selected from the group consisting of halogen, for example fluorine and chlorine, (C1-C4)alkyl, preferably methyl or ethyl, (C1-C4)haloalkyl, preferably trifluoromethyl, (C1-C4)alkoxy, preferably methoxy or ethoxy, (C1-C4)haloalkoxy, nitro and cyano. Especially preferred in this context are substituents methyl, methoxy and chlorine.
Optionally substituted phenyl or phenoxy is preferably phenyl or phenoxy, each of which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals selected from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C1-C4)haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
If substitutions are defined by one or more radicals from among a group of radicals, this encompasses both the substitution by one or more identical radicals and the mono- or polysubstitution by different radicals.
Subject of the invention are also all stereoisomers which are encompassed by formula (I) and their mixtures. Such compounds of the formula (I) contain one or more asymmetric carbon atoms which are not indicated separately in formula (I). The possible stereoisomers which are defined by their specific spatial shape, such as enantiomers or diastereomers, are all encompassed by formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure starting materials. Formula (I) also encompasses tautomers of the compounds stated, inasfar as they are formed by proton migration and are chemically stable.
The compounds of the formula (I) may form salts in which an acidic hydrogen atom is replaced by a suitable cation. These salts are, for example, metal salts; preferably alkali metal salts or alkaline earth metal salts, in particular sodium salts and potassium salts, or else ammonium salts or salts of organic amines. Likewise, salt formation can be effected by an addition reaction of an acid with basic groups, such as amino. Acids which are suitable for this purpose are strong inorganic and organic acids, for example HCl, HBr, H2SO4, HNO3 or formic acid.
Compounds of the formula (I) are successfully synthesized in very good yields and purities starting from compounds of the formula (II) mentioned hereinbelow.
Subject of the present invention is thus also a process for the preparation of compounds of the formula (I) comprising the steps of
1a) reacting a compound of the formula (II) 
xe2x80x83by catalytic hydrogenation in the absence of an acid to give a compound of the formula (III) or by catalytic hydrogenation in the presence of an acid, for example H+Xxe2x88x92, where Xxe2x88x92 is an equivalent of an acid anion, such as halogen, for example Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, or HSO4xe2x88x92, xc2xdSO42xe2x88x92, H2PO4xe2x88x92, xc2xdHOP42xe2x88x92, ⅓PO43xe2x88x92 or xe2x88x92OCOR (where R=H or (C1-C8)alkyl) to give a compound of the formula (IIIa), where Xxe2x88x92 is an equivalent of an acid anion, such as halide, for example Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, or HSO4xe2x88x92, xc2xdSO42xe2x88x92, H2PO4xe2x88x92, xc2xdHPO42xe2x88x92, ⅓PO43xe2x88x92 or xe2x88x92OCOR (where R=H or (C1-C8)alkyl), 
xe2x80x83and subsequently
1b) reacting the compound of the formula (III) or (IIIa) with a sulfonic acid derivative to give a compound of the formula (I) where R2, R3 and R6=H; or
2a) xcex1) reacting a compound of the formula (II) 
xe2x80x83by customary reduction methods for nitro compounds to give a compound of the formula (IV), 
xe2x80x83and subsequently
xe2x80x83xcex2) reacting the compound of the formula (IV) either by catalytic hydrogenation or by customary reduction methods for nitriles to give a compound of the formula (III) or (IIIa),
xe2x80x83and subsequently
2b) reacting the compound of the formula (III) or (IIIa) with a sulfonic acid derivative to give a compound of the formula (I) where R2, R3 and R6=H; or
3a) xcex1) reacting a compound of the formula (II) 
xe2x80x83by customary reduction methods for nitrites to give a compound of the formula (V) or (Va), where X{circle around (xe2x88x92)} is as defined in formula (IIIa), 
xe2x80x83and subsequently
xe2x80x83xcex2) reacting the compound of the formula (V) or (Va) by customary reduction methods for nitro compounds or by catalytic hydrogenation to give a compound of the formula (III) or (IIIa),
xe2x80x83and subsequently
3b) reacting the compound of the formula (III) or (IIIa) with a sulfonic acid derivative to give a compound of the formula (I) where R2, R3 and R6=H; or
4a) xcex1) reacting a compound of the formula (II) 
xe2x80x83by customary reduction methods for nitrites to give a compound of the formula (V) or (Va), where Xxe2x88x92 is as defined in formula (IIIa), 
xe2x80x83xcex2) and subsequently reacting the compound of the formula (V) or (Va) with a sulfonic acid derivative to give a compound of the formula (VI), 
xe2x80x83and subsequently
4b) reacting the compound of the formula (VI) by customary reduction methods for nitro compounds or by catalytic hydrogenation to give a compound of the formula (I) where R2, R3 and R6=H.
The compounds of formulae (III), (IIIa), (V), (Va) and (VI) are novel and also subject of the present invention.
Compounds of the formula (I) where R2 and/or R3=acyl can be obtained by acylating compounds of the formula (I) where R2 and R3=H with acylating agents such as carbonyl halides, sulfonyl halides and carbamoyl halides, carboxylic anhydrides, sulfonic anhydrides, haloformic esters or isocyanates, by customary methods (see, for example, L.-F. Tietze, Th. Eicher, Reaktionen und Synthesen im organisch-chemischen Praktikum [Reactions and Syntheses in the Organochemical Laboratory Practical], Thieme Verlag Stuttgart/New York, 1981, pp. 131, 316, 318, 345; R. C. Larock, Comprehensive Organic Transformations (1989), pp. 979, 981). Examples of suitable solvents are aprotic solvents such as dichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene or chlorobenzene, preferably at temperatures of from 0xc2x0 C. to the boiling point of the solvent.
Compounds of the formula (I) where R6=unsubstituted or substituted C1-C8-alkyl can be obtained for example by alkylating compounds of the formula (I) where R6=H with alkylating agents such as alkyl halides, alkyl sulfates such as dimethyl sulfate or alkyl tosylates by customary methods. Examples of suitable solvents are acetone and dimethylformamide (cf., for example, R. C. Larock, Comprehensive Organic Transformations (1989), p. 398; L.-F. Tietze, Th. Eicher, Reaktionen und Synthesen im organisch-chemischen Praktikum, Thieme Verlag Stuttgart/New York, 1981, p. 75; Organikum, Organisch-chemisches Grundpraktikum [Basic Laborary Practical in Organic Chemistry] VEB, Berlin 1981). The alkylation can be carried out in the presence of bases such as K2CO3, NaH or alkoxides such as sodium alkoxide. The starting material is preferably compounds of the formula (I) in which R2 and R3 are acyl.
Compounds of the formula (I) where R6=unsubstituted or substituted C1-C8-alkyl can also be obtained for example via reductive aminations, for example with aldehydes or ketones in the presence of reducing agents such as H2/catalyst, formic acid, zinc/HCl, sodium borohydride or sodium cyanoborohydride. An example is the Leuckard-Wallach reaction with formaldehyde and formic acid.
Preferred processes are those in which the nitro and the nitrile group in compounds of the formula (II) are reduced jointly in one process step by means of catalytic hydrogenation in accordance with process variant 1a) to give compounds of the formula (III) or (IIIa).
The amino compounds of the formulae (III) and (V) which are obtained as intermediates in the process according to the invention can also arise in the form of their salts (IIIa) and (Va) and can be reacted further when the reaction or work-up is effected in an acidic medium.
The symbols given in formulae (II), (III), (IIIa), (IV), (V), (Va) and (VI) have the same meaning as in formula (I), including the preferred ranges mentioned herefor. Preferred compounds of the formulae (II), (III), (IIIa), (IV), (V), (Va) and (VI) are those in which the groups xe2x80x94CN (formulae (II) and (IV)), xe2x80x94CH2xe2x80x94NH2 (formulae (III) and (V)), xe2x80x94CH2xe2x80x94NH3+Xxe2x88x92 (formulae (IIIa) and (Va)) and xe2x80x94CH2xe2x80x94NR6xe2x80x94SO2xe2x80x94R7 (formula (VI)) are in the para position relative to the group xe2x80x94COxe2x80x94OR1.
Furthermore, substeps of the process according to the invention are also subject of the invention.
The compounds of the formula (II) are known, cf., for example, DE 22 39 799 C3 or Journal of the American Chemical Society 99, 6721 (1977).
The catalytic hydrogenation of the compound of the formula (II) by process variant 1a), of the compound of the formula (IV) by process variant 2axcex2), of the compound of the formula (V) or (Va) by process variant 3axcex2) or of the compound of the formula (VI) by process variant 4b) is successfully carried out by means of customary hydrogenation methods. Examples of hydrogen sources which can be used are hydrogen gas, hydrazine or HNxe2x95x90NH. Particularly suitable hydrogenation catalysts are noble-metal catalysts, for example Pd, Pt, Rh, Ir or Ni or Co catalysts. The noble metals can be used in elemental form or in the form of oxides or halides. The noble-metal catalysts can be used as desired without or, preferably, with support materials such as active charcoal, kieselguhr, silicates.
The hydrogenation can be carried out both by atmospheric pressure and by applying a superatmospheric hydrogen pressure, as a rule between 1 and 100 bar, preferably 1-50 bar. In general, the suitable temperature is in the range of from xe2x88x9220 to 150xc2x0 C., preferably between 0 and 120xc2x0 C.
Examples of solvents which are suitable for the hydrogenation are solvents of the groups water, alcohols such as methanol or ethanol, ethers such as diethyl ether, tetrahydrofuran or dioxane, amides such as dimethylformamide or dimethylacetamide, esters such as ethyl acetate, organic carboxylic acids such as formic acid or acetic acid, aromatic hydrocarbons such as toluene, xylene and chlorobenzene, or halogenated aliphatic hydrocarbons such as CH2Cl2, it being possible to employ the solvents in pure form or as mixtures.
The catalytic hydrogenation of the compounds of the formula (II) by process variant 1a) or of the compounds of the formula (IV) by process variant 2axcex2) is preferably carried out in the presence of 1-10 molar equivalents of an acid. Solvents which are preferably used are alcohols such as methanol or ethanol, or water. Examples of suitable acids are inorganic acids or carboxylic acids. Preferred are acids of the formula H+Xxe2x88x92 where Xxe2x88x92 is an equivalent of an acid moiety, such as halogen for example Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, or HSO4xe2x88x92, xc2xdSO42xe2x88x92, H2PO4xe2x88x92, xc2xdHPO42xe2x88x92, ⅓PO43xe2x88x92 or xe2x88x92OCOR (where R=H or (C1-C8)alkyl), for example hydrohalic acids such as hydrochloric acid or hydrobromic acid, or sulfuric acid, phosphoric acid, formic acid or acetic acid. If, for example, the two last-mentioned acids are used, the acids may also fully assume the role of the solvent.
The catalytic hydrogenation of the compounds of the formula (IV) can also be carried out by using 1-10 molar equivalents of ammonia, nickel or cobalt catalysts such as Raney nickel or Raney cobalt preferably being employed. Solvents which are preferably used in this context are alcohols such as methanol or ethanol.
The reduction of the nitro group in compounds of the formula (II) by process variant 2axcex1), compounds of the formulae (V) and (Va) by process variant 3axcex2) or compounds of the formula (VI) by process variant 4b) can be carried out with customary reducing agents for aromatic nitro compounds. Such reducing agents and reaction conditions are described, for example, in R. C. Larock, Comprehensive Organic Transformations (1989) pp. 411-415, VCH Publishers Inc. and the literature cited therein. Examples of preferred reducing agents are Fe, Zn, Sn or their salts such as FeSO4 or Sn-II salts such as SnCl2. Examples of suitable solvents are organic carboxylic acids, alcohols and/or mineral acids. In general, the reaction temperature is between 0xc2x0 C. and the boiling point of the solvent.
The reduction of the nitrile group in compounds of the formula (IV) by process variant 2axcex2) and compounds of the formula (II) by process variant 3axcex1) and 4axcex1) can be carried out by customary reducing agents for nitrites. Such reducing agents and reaction conditions are described, for example, in R. C. Larock, Comprehensive Organic Transformation (1989) pp. 437-438, VCH Publishers Inc. and the literature cited therein. Examples of preferred reducing agents are boron hydride compounds or aluminum hydride compounds such as BH3/THF, BH3/DMS and their salts such as NaBH4. Examples of suitable solvents are ethers such as dioxane or tetrahydrofuran. The reaction temperature is generally between 0xc2x0 C. and the boiling point of the solvent. If the reduction product is subsequently worked up in an acid medium, for example methanol/HCl, the compound of the formula (III) (process variant 2axcex2) or the compound of the formula (V) (process variants 3axcex1 and 4axcex1) can be obtained in the form of a salt of the formula (IIIa) or (Va), respectively, which can be reacted further analogously to compound (III) or compound (V), respectively.
The acylation of the compounds of the formula (III) or (IIIa) by process variant 1b), 2b) or 3b) or of the compounds of the formula (V) or (Va) by process variant 4axcex2) with a sulfonic acid derivative can be carried out under customary conditions for acylation reactions to give the compounds of the formula (VI) in the case of compounds of the formula (V) or (Va) or to give the compounds of the formula (I) according to the invention in the case of compounds of the formula (III) or (IIIa).
For example, compounds of the formula (III) or (IIIa), or (V) or (Va), are reacted in suitable solvents with sulfonic acid derivatives in the presence of bases as acid acceptors to give compounds of the formula (I) or (VI) respectively. Examples of solvents which are suitable for the acylations are solvents from the groups water, alcohols such as methanol or ethanol, halogenated aliphatic hydrocarbons such as CH2Cl2, aromatic hydrocarbons such as toluene, chlorobenzene or xylene, ethers such as diethyl ether, tetrahydrofuran or dioxane, ketones such as acetone or methyl isobutyl ketone, esters such as ethyl acetate, and aprotic solvents such as acetonitrile, dimethylformamide or dimethylacetamide, it being possible for the solvents to be employed in pure form or as mixtures. Preferred are water and mixtures of water and water-soluble organic solvents from the abovementioned groups.
Bases which are suitable are inorganic or organic bases, for example carbonates such as K2CO3, Na2CO3 or NaHCO3, alkali metal hydroxides and alkaline earth metal hydroxides such as NaOH, KOH or Ca(OH)2, or amines such as triethylamine. In general, the bases are employed in amounts of 1-10 molar equivalents, preferably 1-5 molar equivalents, per compound of the formula (III) or (V); when compounds of the formula (IIIa) or (Va) are employed, the minimum amount of the base employed is at least two molar equivalents.
Examples of suitable sulfonic acid derivatives are sulfonyl halides such as fluorides, chlorides, bromides or iodides, and sulfonic anhydrides. Preferred are sulfonic acid derivatives of the formula R7xe2x80x94SO2xe2x80x94Z, where R7 is defined as in formula (I), and Z is a leaving group such as halogen (for example fluorine, chlorine, bromine or iodine) or Oxe2x80x94SO2xe2x80x94RZ, where RZ is as defined for R7 in formula (I). The acylation is carried out for example in such a way that the compounds of the formula (III) or (IIIa), or (V) or (Va), are reacted with the sulfonic acid derivatives in suitable solvents in the presence of a suitable base, in general at temperatures of from xe2x88x9220 to 100xc2x0 C. Preferred are temperatures of from xe2x88x9210 to 50xc2x0 C. The amounts of sulfonic acid derivatives are generally 1-10 molar equivalents, preferably 1-5 molar equivalents, per compound of the formula (III) or (IIIa), or (V) or (Va).
In addition to compounds of the formula (I) and their preparation, the present invention also relates to their further reaction to give compounds of the formulae (VII) and (VIII). To do this, compounds of the formula (I) where R2 and/or R3=acyl must first be converted by customary methods into compounds of the formula (I) where R2xe2x95x90R3xe2x95x90H, and these are then further reacted to give compounds of the formulae (VII) and (VIII). The symbols used in formulae (VII) and (VIII) have the same meanings as stated for formula (I), including the preferred ranges stated herefor, and Y in formula (VII) is halogen such as fluorine, chlorine, bromine or iodine. Preferred compounds of the formulae (VII) and (VIII) are those in which the group xe2x80x94CH2xe2x80x94NR6xe2x80x94SO2xe2x80x94R7 is in the para position relative to the group xe2x80x94COxe2x80x94OR1. 
As is described in (EP-A-723 534), compounds of the formulae (VII) and (VIII) are suitable precursors for the preparation of potent herbicidal sulfonylureas, the preparation of the compounds of the formulae (VII) and (VIII) being especially efficient in the present process according to the invention and the compounds of the formulae (VII) and (VIII) being obtained in very good yields and purities.
Methods for the conversion 6) of anilines into sulfonyl halides are known (see, for example, H. Meerwein et al., Chem. Berichte 90, 841-852 (1957)). Surprisingly, compounds of the formula (I) where R2, R3xe2x95x90H are successfully reacted to give compounds of the formula (VII) on the basis of procedures described in the literature. Thus, compounds of the formula (I) where R2, R3xe2x95x90H can be diazotized under suitable conditions and subsequently coupled with suitable SO2 sources, such as SO2 gas, Na2S2O5 or NaHSO3 in the presence of acids such as carboxylic acids, for example acetic acid, or inorganic acids, for example hydrohalic acids HY such as HCl or HBr, and catalysts, for example copper catalysts based on Cu(I) and/or Cu(II) salts to give sulfonyl halides of the formula (VII).
The diazotization can be carried out with suitable diazotizing agents such as NaNO2 in the presence of acids such as inorganic acids, preferably hydrohalic acids HY, such as HCl or HBr. The solvent used is preferably a water/acid mixture, in particular a mixture of water/carboxylic acid (for example acetic acid) or water/mineral acid (for example hydrohalic acid HY such as HCl or HBr). In general, the reaction temperature is xe2x88x9220 to 50xc2x0 C., preferably xe2x88x9210 to 20xc2x0 C.
The following are examples which can be used as solvents for the subsequent coupling reaction: water, carboxylic acids such as acetic acid, carboxylic esters such as ethyl acetate, ethers such as diethyl ether, tetrahydrofuran or dioxane, halogenated aliphatic hydrocarbons such as CH2Cl2 or dichloroethane, aromatic hydrocarbons such as toluene, chlorobenzene or xylene, or ketones such as acetone or methyl isobutyl ketone. Moreover, the reaction mixture contains acids, for example carboxylic acids such as acetic acid or mineral acids such as hydrohalic acids HY, for example HCl or HBr, which are either still present from the diazotization reaction and/or are added when the coupling reaction is carried out. Examples of SO2 sources which can be used are, for example, SO2 gas (1-10 equivalents), Na2S2O5 (1-10 equivalents) or NaHSO3 (1-10 equivalents), in the presence of catalysts, for example copper catalysts such as CuCl (1-20 mol %), CuCl2 (1-20 mol %), CuBr (1-20 mol %) or CuBr2 (1-20 mol %).
Starting from sulfonyl halides of the formula (VII) the aminolysis 7) which yields sulfonic amides of the formula (VIII) is, surprisingly, successfully carried out with high efficiency and in high yields by reacting compounds of the formula (VII) for example in suitable solvents with ammonia.
The aminolysis can be carried out with suitable reagents, for example 2-10 molar equivalents of aqueous ammonia solution or NH3 gas in the presence of a solvent, for example ketones such as acetone or methyl isobutyl ketone, halogenated aliphatic hydrocarbons such as CH2Cl2, aromatic hydrocarbons such as xylene, toluene or chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or dioxane, esters such as ethyl acetate, aprotic solvents such as dimethylformamide, dimethylacetamide or acetonitrile, or mixtures of these solvents. In general, the reaction temperature is from xe2x88x9210 to 100xc2x0 C., preferably xe2x88x9210 to 40xc2x0 C., especially preferably xe2x88x9210 to 20xc2x0 C.
The compounds of the formulae (VII) and (VIII) can subsequently be reacted in various ways to give sulfonylureas, preferably sulfonylureas of the formula (XIII) and/or their salts, for example by
8) reacting a sulfonyl halide of the formula (VII) with a cyanate MOCN, in which M is an ammonium ion or an alkali metal ion such as Li, Na or K, and with an amino heterocycle of the formula (XII) in the presence of a base to give the sulfonylurea; or 
9) reacting a compound of the formula (VIII) with a heterocyclic carbamate of the formula (IX), in which Ph is unsubstituted or substituted phenyl to give the sulfonylurea; or 
10) a) first reacting an amino heterocycle of the formula (XII) in the presence of a base such as trialkylamine, for example triethylamine, with phosgene to give a heterocyclyl isocyanate of the formula (X), and b) reacting the heterocyclyl isocyanate formed, of the formula (X), with a phenylsulfonamide of the formula (VIII) to give the sulfonylurea; or 
11) a) reacting a compound of the formula (VIII) with an alkyl isocyanate, for example RNCO, in which R=C1-C10-alkyl and with phosgene to give a sulfonyl isocyanate of the formula (XI), and b) reacting the sulfonyl isocyanate formed, of the formula (XI), with an amino heterocycle of the formula (XII) to give the sulfonylurea; or 
12) a) reacting a compound of the formula (VIII) with a carbonic acid derivative such as Rxe2x80x94COxe2x80x94OPh, in which Ph=unsubstituted or substituted phenyl and R=halogen or unsubstituted or substituted phenoxy to give a phenylsulfonyl carbamate of the formula (XIV), and b) reacting the phenylsulfonyl carbamate formed, of the formula (XIV), in which Ph=unsubstituted or substituted phenyl, with an amino heterocycle of the formula (XII) to give the sulfonylurea. 
The symbols used in formulae (IX), (X), (XI), (XII), (XIII) and (XIV) have the same meaning as stated in formula (I), including the preferred ranges stated herefor; in addition, the following meanings are also used therein:
Rx, Ry independently of one another are a hydrogen atom, halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, where each of the last-mentioned 3 radicals is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)alkoxy and (C1-C4)alkylthio, or are mono- or di[(C1-C4)alkyl]amino, (C2-C6)alkenyl, (C2-C6)alkynyl, (C3-C6)alkenyloxy or (C3-C6)alkynyloxy,
X is CH or N, and
Y is halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine.
Preferred compounds of the formulae (XI), (XIII) and (XIV) are those in which the group xe2x80x94CH2xe2x80x94NR6xe2x80x94SO2xe2x80x94R7 is in the para position relative to the group xe2x80x94COOR1.
Sulfonylureas such as the compounds of the formula (XIII) can form salts in which the hydrogen of the xe2x80x94SO2xe2x80x94NHxe2x80x94 group is replaced by an agriculturally suitable cation. Examples of these salts are metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium salts and potassium salts, or else ammonium salts or salts with organic amines. Likewise, salt formation can be effected by an addition reaction of an acid with basic groups, such as, for example, amino and alkylamino. Acids which are suitable for this purpose are strong inorganic and organic acids, for example HCl, HBr, H2SO4 or HNO3. If the present description mentions sulfonylureas such as the compounds of the formula (XIII), this is also to be understood as including their salts in each case.
In process variant 8), the reaction of the sulfonyl halides (VII) is carried out with amino heterocycles of the formula (XII) and cyanates MOCN preferably with base catalysis in inert aprotic organic solvents such as ethyl acetate, tetrahydrofuran, toluene or acetonitrile between 0xc2x0 C. and the boiling point of the solvent. Examples of suitable bases are organic amine bases, in particular pyridines such as pyridine or 3-methylpyridine.
In process variant 9), the reaction of the compounds of the formulae (VIII) and (IX) is carried out preferably with base catalysis in an inert organic solvent such as dichloromethane, acetonitrile, dioxane, tetrahydrofuran or ethyl acetate at between 0xc2x0 C. and the boiling point of the solvent. Examples of bases which are used are K2CO3 or organic amine bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
In process variant 10), the reaction of the compound of the formula (XII) is carried out with phosgene to give heterocyclyl isocyanates of the formula (X), for example in inert organic solvents such as ethyl acetate, dioxane or aromatic solvents such as chlorobenzene, if appropriate with addition of an organic amine base such as triethylamine, in general between 0xc2x0 C. and the boiling point of the solvent. The subsequent reaction of the compound of the formula (X) with the compound of the formula (VIII) is carried out for example in inert solvents such as ethyl acetate, dioxane or aromatic solvents such as chlorobenzene, preferably in the presence of bases such as K2CO3 or trialkylamines such as triethylamine or tributylamine, in general at temperatures of from xe2x88x9220xc2x0 C. to the boiling point of the solvent (cf. for example, EP-A-232 067 or EP-A-166516).
In process variant 11), the reaction of the compound of the formula (VIII) is carried out with an alkyl isocyanate and phosgene to give phenylsulfonyl isocyanates of the formula (XI), for example in inert solvents such as dichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene or chlorobenzene, in general at temperatures of from 20xc2x0 C. to the boiling point of the solvent. The subsequent reaction of the compound of the formula (XI) with amino heterocycles of the formula (XII) is carried out for example in inert solvents such as dichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene or chlorobenzene, in general at temperatures of from 0xc2x0 C. to the boiling point of the solvent (cf. for example U.S. Pat. No. 4,481,029).
In process variant 12), the reaction of the compound of the formula (VIII) with a carbonic acid derivative, for example diphenyl carbonate or phenyl chloroformate, to give a phenylsulfonyl carbamate of the formula (XIV) is carried out for example in inert solvents such as xylene, dichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene or chlorobenzene, preferably in the presence of a base such as K2CO3 or organic amine bases such as triethylamine, preferably at temperatures of from 20xc2x0 C. to the boiling point of the solvent (cf., for example, U.S. Pat. No. 4,684,393 and U.S. Pat. No. 4,743,290). The subsequent reaction of the compound of the formula (XIV) with amino heterocycles of the formula (XII) is carried out for example in inert solvents such as xylene, dichloromethane, acetonitrile, dioxane, tetrahydrofuran, toluene or chlorobenzene, in general at temperatures of between 20xc2x0 C. and the boiling point of the solvent.
The compounds of the formula (I) according to the invention thus make possible an efficient preparation of herbicidal sulfonylureas and other active substances.